铜离子荧光探针的研究进展

高选择性、超灵敏性铜离子荧光探针的设计和开发,在环境检测、食品安全及人体内微量铜元素探测等领域具有重要意义。本文根据荧光分子探针对铜离子的识别机制和化学结构特点,从罗丹明、香豆素、芘基团、萘酰亚胺、氟硼吡咯及其他荧光基团等发色团出发,综述了近年来铜离子荧光探针的研究进展。参考文献27篇。     

基于萘酰亚胺的次氯酸荧光探针的合成及细胞成像性能研究

以萘酰亚胺结构为荧光发色团,设计开发了一种含C=C双键的、具有分子内电荷转移(ICT)效应的新型水溶性优化的次氯酸荧光探针3-(2-氰基丙烯酸乙酯基)-4-羟基-N-正丙基-1,8-萘酰亚胺(NAEC).添加次氯酸后,探针分子NAEC中的C=C双键被氧化,生成醛基,探针NAEC原有的ICT效应被破坏,产生荧光信号.经核磁、质谱、荧光发射光谱和UV-Vis吸收光谱对其结构和检测性能进行了研究.结果表明,在pH=7.4的N,N-二甲基甲酰胺(DMF)/磷酸缓冲盐溶液(PBS)(V∶V=1∶19)缓冲体系中,探针NAEC可在10s内完成对次氯酸的检测,荧光分析检测限为2.4nmol/L,斯托克斯位移为100nm;探针NAEC显示出较强的抗干扰性,能在其他活性氧、小分子生物硫醇及常见阴离子等22种干扰物存在下完成次氯酸的专一检测.同时,该探针分子的膜透性与生物相容性良好,具备较好的活体内源性ClO-荧光成像能力,在生物检测及环境监控等领域具有良好的应用前景.     

非猝灭型Cu2+荧光分子探针的研究进展

Cu2+荧光分子探针的开发对高灵敏及高选择性检测Cu2+具有重要意义.本文按照探针的结构类型,综述了近些年来荧光增强及比率型Cu2+荧光分子探针的研究进展.引用文献40篇.     

新型荧光/EPR双功能次氯酸探针的构建及性能

构建了一种新型香豆素-萘酰亚胺荧光/电子顺磁共振双功能探针CNNOH,并结合荧光光谱、电子顺磁共振(EPR)波谱和紫外-可见吸收光谱对其性能进行了研究.结果表明,该探针可结合荧光光谱的灵敏性和EPR波谱的特异性进行次氯酸的检测;由于香豆素与萘酰亚胺之间存在荧光共振能量转移(FRET)效应,探针分子具有较大的Stokes位移(135 nm),可有效避免由激发光导致的杂散光对检测的干扰.该双功能探针具有检出限低(0.214μmol/L)、反应速度快(~10 s)、检测范围宽(0~5 mmol/L)、选择性好及在生理条件下稳定的特点,预期在活体细胞检测方面有良好的应用前景.     

基于1,8-萘酰亚胺的半胱氨酸荧光探针的合成及在生物成像方面的应用

设计合成了一种用于检测半胱氨酸的新型荧光探针乙二醛(N-羟乙基-1,8-二甲酰亚胺-4-萘基)单腙(NAD),该荧光探针对半胱氨酸表现出较高的灵敏度和选择性.当半胱氨酸加入NAD溶液中,会形成分子内氢键,抑制C■N的异构化,导致荧光增强.此外,探针NAD可应用于细胞内半胱氨酸的检测,表明该类型探针在生物检测应用方面具有较大的潜力.     

生物小分子巯基化合物荧光探针研究进展

细胞内的小分子巯基化合物在诸多生理过程中扮演重要角色.分子荧光探针具有灵敏度高、选择性好、生物相容性好、实时原位监测等优点.因此,构建可以选择性检测巯基化合物的荧光探针具有重要的生物学和医学意义.根据荧光探针与巯基化合物的反应类型总结了近几年来小分子巯基化合物荧光探针的设计策略和研究进展.     

一种可用于直接检测空气中异氰酸酯的比率型荧光探针

异氰酸酯是一类广泛使用的化工原料，但容易挥发到空气中对人体健康造成危害.因此，建立一种快速、方便检测空气中异氰酸酯的方法具有重要的意义.合成了一种荧光探针（N-正丁基-4-羟基-1，8萘二酰亚胺），能与异氰酸酯快速反应，从而使探针的荧光颜色由黄绿色转变为蓝色，实现对异氰酸酯的比率型荧光检测.同时，该探针对异氰酸酯的响应具有灵敏性和选择性.反应机理研究表明，探针萘环4位上的羟基与异氰酸酯基（-NCO）反应生成了氨基甲酸酯基团.为了直接检测空气中的异氰酸酯，制备了一种基于该探针的检测试纸，实现对空气中异氰酸酯高灵敏性、高选择性的检测.该方法对空气中异氰酸酯的检测具有实际意义，同时也为挥发性有机物的检测提供了参考.     

前言:分子荧光探针专刊

正随着生命科学的发展和疾病诊断要求的不断提高,高灵敏度、高选择性、快速简便的分析方法越来越受到重视.基于新原理发展用于生物分子检测的新技术和新方法,已经成为现代分析化学研究的主题和热点,对国家经济社会的可持续发展具有重要意义.分子荧光探针具有灵敏度高、操作简便、重现性和膜穿透性好等优点.此外,与荧光成像技术相结合,分子荧光探针适用于生物体系中目标分子的实时原位无损检测,从而实现活细胞与活体中生物分子及其生物过     

基于萘酰亚胺的生物硫醇探针的合成及对含硫醇氨基酸的检测

合成了以4-羟基萘酰亚胺为荧光团,2,4-二硝基苯磺酰氧基为特异性识别基团的生物硫醇探针4-(2,4-二硝基苯磺酰氧基)-正丁基-1,8-萘酰亚胺(DNSBN).吸收光谱和荧光光谱结果表明, DNSBN对半胱氨酸(Cys)、同型半胱氨酸(Hcy)和谷胱甘肽(GSH)3种生物硫醇分子具有高效的检测识别能力,不受其它17种天然氨基酸的干扰.同时,通过荧光滴定实验证实了此探针是一种比率型探针,555 nm处的荧光强度与溶液中的生物硫醇分子浓度在0 ~ 20 μmol/L范围内呈良好的线性关系,对Cys、Hcy和GSH的检出限(3σ)分别为25.9、92.0和77.9 nmol/L.而吸收光谱、荧光光谱和质谱表征数据显示,生物硫醇与2,4-二硝基苯磺酸酯发生亲核取代反应并导致磺酸酯的分解.随着识别基团的解离,探针分子的d-PeT (donor-excited photoinduced electron transfer) 效应被解除,并出现非常明显的比色与荧光变化.HeLa细胞成像实验表明,探针DNSBN具有良好的生物相容性,能够对细胞外源性生物硫醇分子进行检测.     

基于荧光小分子2-氨基-7-甲基-1,8-萘啶对C碱基的识别检测DNA双链中的C/C错配

单碱基错配是单核苷酸多态性(SNPs)的一种,是导致突变的DNA损伤类型之一.单碱基错配的检测对于从分子水平上阐明多种疾病形成的原因,实现基因水平的治疗都是至关重要的前提条件.发展具有高灵敏度、高选择性的单碱基错配检测方法势在必行.常用的单碱基错配检测方法包括凝胶电泳、荧光检测、SPR和质谱检测等.本文采用2-氨基-7-甲基-1,8-萘啶(AMND)作为荧光探针,AMND能嵌入双链DNA(ds-DNA)中的错配位点,并通过氢键识别错配碱基,这一结合过程伴随探针小分子的荧光淬灭,通过检测荧光淬灭现象实现单碱基错配及错配碱基类型的识别,建立了SNPs荧光分型方法.     

Synthesis of fluorescent probes based on stilbenes and diphenylacetylenes targeting β-amyloid plaques

Three fluorescent probes were synthesized aiming for optical imaging to detect amyloid plaques present in the patients with Alzheimer’s disease (AD). These compounds were prepared via Sonogashira coupling of a well-defined fluorophore (4-bora-3a,4a-diaza-s-indacene, BODIPY) with the pharmacophore possessing either a stilbene or a diphenylacetylene moiety. Different polyethylene glycol chain lengths were used as linkers between the fluorophore and the pharmacophore to adjust the lipophilicity of these probes. These compounds exhibit strong fluorescence emission between 665 and 680 nm and have very high extinction coefficients comparable to the parent fluorophore, BODIPY dye.     

BODIPY 493 acts as a bright buffering fluorogenic probe for super-resolution imaging of lipid droplet dynamics

The need for temporal resolution and long-term stability in super-resolution fluorescence imaging has motivated research to improve the photostability of fluorescent probes. Due to the inevitable photobleaching of fluorophores, it is difficult to obtain long-term super-resolution imaging regardless of the self-healing strategy of introducing peroxide scavengers or the strategy of fluorophore structure modification to suppress TICT formation. The buffered fluorogenic probe uses the intact probes in the buffer pool to continuously replace the photobleached ones in the target, which greatly improves the photostability and enables stable dynamic super-resolution imaging for a long time. But the buffering capacity comes at the expense of reducing the number of fluorescent probes in targets, resulting in low staining fluorescence intensity. In this paper, we selected BODIPY 493, a lipid droplet probe with high fluorescence brightness, to explore the dynamic process of lipid droplet staining of this probe in cells. We found that BODIPY 493 only needs very low laser power for lipid droplet imaging due to the high molecular accumulation in lipid droplets and the high brightness, and the spatiotemporal resolution is greatly improved. More importantly, we found that BODIPY 493 also has a certain buffering capacity, which enables BODIPY 493 to be used for super-resolution imaging of lipid droplet dynamics. This work reminds researchers to coordinate the buffering capacity and brightness of fluorogenic probes.     

具有大斯托克位移的荧光探针分子

用荧光法来监视多个生理参数时,需要几个不同的荧光探针分子.这些探针分子要被同一波长激发,但是具有明显分离的、不同的发射波长.目前,大多数荧光探针只有小的斯托克位移(50-90 nm),从而限制了它们在多个物质同时检测上的应用.在这项工作中,我们提出了一个新的分子探针设计:受体-荧光分子1-间隔-荧光分子2(简称RFSF...     

氨基苯基类中氮茚化合物的合成及作为质子探针的研究

设计合成了3个氨基苯基类中氮茚化合物, 研究了其在不同pH值的缓冲溶液中的荧光强度变化. 结果表明， 在pH=2.1～4.2之间， 该类化合物具有荧光敏感性. 化合物3a和3b可以作为良好的质子控制的荧光开关器件信号分子.     

A simple FRET-based modular design for diagnostic probes

In recent years, there has been a massive effort to develop molecular probes with optical modes of action. Probes generally produce detectable signals based on changes in fluorescence properties. Here, we demonstrate the potential of self-immolative molecular adaptors as a platform for Turn-On probes based on the FRET technique. The probe is equipped with identical fluorophore pairs or a fluorophore/quencher FRET pair and a triggering substrate. Upon reaction of the analyte of interest with the triggering substrate, the self-immolative adaptor spontaneously releases the two dye molecules to break off the FRET effect. As a result, a new measurable fluorescent signal is generated. The fluorescence obtained can be used to quantify the analyte. The modular structure of the probe design will allow the preparation of various chemical probes based on the FRET activation technique.     

Activatable imaging probes with amplified fluorescent signals

Current optical imaging probe applications are hampered by poor sensitivity and specificity to the target, but molecular-level fluorescent signal activation strategies can efficiently overcome these limitations. Recent interdisciplinary research that couples the imaging sciences to fluorophore, peptide, polymer, and inorganic-based chemistry has generated novel imaging probes that exhibit high sensitivity and low background noise in both in vitro and in vivo applications. This feature article introduces and discusses the various approaches described by the term "fluorescent signal activation methods" with respect to their unique imaging probe design strategies and applications.     

基于罗丹明的重金属和过渡金属阳离子荧光分子探针研究进展

介绍了近五年来以罗丹明为母体的重金属和过渡金属阳离子荧光分子探针领域的研究进展.文中按照荧光团和识别基团之间连接臂的不同对国内外各研究组的工作进展进行归类总结,并对探针设计的思路、探针的性质和应用给出了简要介绍.     

Fluorescence-quenching phenomenon by photoinduced electron transfer between a fluorescent dye and a nucleotide base.

Fluorescently labeled oligonucleotide probes have been widely used in biotechnology, and fluorescence quenching by the interaction between the dyes and a nucleobase has been pointed out. This quenching causes big problem in analytical methods, but is useful in some other cases. Therefore, it is necessary to estimate the fluorescence quenching intensity under various conditions. We focused on the redox properties of some commercially available fluorescent dyes, and investigated dye-nucleotide interactions between a free dye and a nucleotide in aqueous solution by electrochemical and spectroscopic techniques. Our results suggested that the quenching was accompanied by photoinduced electron transfer between a thermodynamically quenchable excited dye and a specific base. Several kinds of fluorescent dyes labeled to the 5'-end of oligonucleotide C10T6 were prepared, and their quenching ratios compared upon hybridization with the complementary oligonucleotide A6G10. The quenching was completely reversible and their efficiencies depended on the attached fluorophore types. The fluorescence of 5-FAM, BODIPY FL or TAMRA-modified probe was strongly quenched by hybridization.     

Selective and sensitive fluorescence "turn-on" Zn~(2+) probes based on combination of anthracene,diphenylamine and dipyrrin

Two fluorescence "turn-on" Zn~(2+) probes were developed by introducing an anthracenyl fluorophore through the linkage of a diphenylamino moiety at the 5-position of a dipyrrin moiety.Thus,two compounds with weak fluorescence were designed,synthesized,and employed as CHEF(chelation enhanced fluorescence) type fluorescence "turn-on" Zn~(2+) probes,which exhibit dramatic fluorescence enhancement upon addition of Zn~(2+),showing high sensitivities and impressive detection limits of 13 and12 nM,respectively,better than their analogues containing simple aryl substituents at the 5 positions of a di-or tripyrrin moiety.In addition,both of the probes exhibit good selectivity,short response time of less than 10 s and wide applicable pH ranges.Furthermore,the weak fluorescence nature of the probes was rationalized based on viscosity dependence measurements and theoretical calculations.These results provide further insight into the development of selective and sensitive zinc probes.     

Carbon nanotube-quenched fluorescent oligonucleotides: probes that fluoresce upon hybridization

We report an effective, novel self-assembled single-wall carbon nanotube (SWNT) complex with an oligonucleotide and demonstrate its feasibility in recognizing and detecting specific DNA sequences in a single step in a homogeneous solution. The key component of this complex is the hairpin-structured fluorescent oligonucleotide that allows the SWNT to function as both a "nanoscaffold" for the oligonucleotide and a "nanoquencher" of the fluorophore. Given this functionality, this carbon nanotube complex represents a new class of universal fluorescence quenchers that are substantially different from organic quenchers and should therefore have many applications in molecular engineering and biosensor development. Competitive binding of a DNA target and SWNTs with the oligonucleotide results in fluorescence signal increments relative to the fluorescence without a target as well as in marked fluorescence quenching. In contrast to the common loop-and-stem configuration of molecular beacons (MBs), this novel fluorescent oligonucleotide needs only one labeled fluorophore, yet the emission can be measured with little or no background interference. This property greatly improves the signal-to-background ratio compared with those for conventional MBs, while the DNA-binding specificity is still maintained by the MB. To test the interaction mechanisms of the fluorescent oligonucleotide with SWNTs and target DNA, thermodynamic analysis and fluorescence anisotropy measurements, respectively, were applied. Our results show that MB/SWNT probes can be an excellent platform for nucleic acid studies and molecular sensing.